Premium
Bifunctional even‐electron ions: 1—Fragmentation behaviour of ω‐methoxy‐, ω‐hydroxy‐ and ω‐chloro‐oxonium ions
Author(s) -
Záhorszky U. I.
Publication year - 1985
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210201008
Subject(s) - oxonium ion , bifunctional , chemistry , moiety , fragmentation (computing) , ion , alkyl , side chain , medicinal chemistry , stereochemistry , organic chemistry , catalysis , polymer , computer science , operating system
Bifunctional oxonium ions—generated from tertiary aliphatic alcohols containing an additional hydroxy, methoxy or chloro group at the end of an alkyl side‐chain—do not markedly exhibit fragmentations typical of ordinary oxonium ions, but show as the main reactions those caused by functional group interaction, through‐space interaction being the dominant factor. The main primary fragmentation is loss of the additional functional group X as HX, followed by loss of the side‐chain originally separating the two functional groups, leading to carbonyl cations. This typical reaction sequence is initiated by proton migration from the oxonium moiety to the additional functional group. The reaction behaviour of the bifunctional ions is discussed. The lowest homologues show specific deviations from the general fragmentation behaviour.